Morpholides of epoxidized fatty acids



NOV. 23, c MAGNE ETAL MORPHOLIDES OF EPOXIDIZED FATTY ACIDS Filed Jan. 15, 1962 INVENTORS FRANK C. MAGNE EVALD L. SKAU ROBERT R. MOD

BY K W I ATTORNEY United States Patent MDREHQLIDES 0F EPUPHDEZED FATTY AQEBS Frank C. Magne, Evald L Shaw, and Robert R. Mod,

New {)rleans, L2,, assignors to the United States of America as represented by the Secretary of Agriculture Filed Jan. 15, 1962, Ser. No, 166,742 3 Claims. (Cl. 2d)-247.7)

(Granted under Title 35, US. (lode (1952), sec. ass

A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to unique mixed morpholides. More particularly, the invention provides the morpholides of mixtures of long chain saturated and unsaturated fatty acids and the epoxy derivatives thereof that can reproducihly be produced from the fatty acids found in natural glycerides. These mixed morpholides are efiicient primary solvent plasticizers exhibiting good compatibility with polymers and copolymers of vinyl chloride.

A morpholide of an acid is an amide of the acid in which the amido nitrogen atom is a nitrogen atom of a morpholine ring. Prior workers have produced the morpholides and other amides of various individual fatty acids and mixtures of fatty acids. Many of the fatty acid amides heretofore produced, e.g., those disclosed in US. Patents 1,986,854; 2,339,056; and 2,380,925; are solvent plasticizers for hydrophilic vinyl resins, such as the polyvinyl acetal resins.

A compound which is a solvent plasticizer for, and thus is compatible with, a hydrophilic vinyl resin such as a polyvinyl acetal resin, exhibits only a very limited compatibility with a hydrophobic vinyl resin such as polyvinyl chloride. If a resin is plasticized with a compound with which it has only a limited compatibility the plasticizer soon exudes or migrates to the surface unless the plasticizer is used in limited amount, or is used in conjunction with a mutual solvent, to obtain adequate compatibility.

As might be expected from the known compatibility of various morpholides of fatty acids with the polyvinyl acetals, the morpholide mixtures from glyceride oil acids such as cottonseed oil acids or peanut oil acids are highly incompatible with polymers of vinyl chloride, even when used as a secondary plasticizer with an equal amount of a highly compatible plasticizer. Similarly, the morpholide of palmitic acid and the morpholide of stearic acid have been found to be highly incompatible When used as plasticizers for vinyl chloride resins, exhibiting migration to the surface within 36 hours. However, in accordance with the present invention, it has been discovered that the morpholides of the unique mixtures of fatty acids, defined below, exhibit good compatibility with vinyl chloride resins.

The term vinyl chloride resins is used throughout the specification and claims to refer to polymers and copolymers of monomers containing vinyl chloride in a predominant proportion in parts by weight. Terms such as good compatibility, compatible, and compatible plasticizers in reference to plasticizers for vinyl chloride resins are used throughout the specification to refer to plasticizers which show no signs of exudation or migration to the surface for at least days when the plasticizer is present in the proportion of about 70 parts per 100 parts by weight of vinyl chloride resin.

The primary object of the present invention is to provide mixed morpholides which are good primary solvent plasticizers for vinyl chloride resins, and which are plasticizers that can economically be produced from fatty acids obtainable from glyceridic oils and fats.

3,2195% Patented Nov. 23, 1965 In order that the invention be readily understood, reference is made to the following description and to the accompanying drawing, the single figure of which constitutes a ternary diagram of morpholides of mixed fatty acids defining compositions according to the invention.

The mixed morpholides provided by this invention exhibit good compatibility with polymers and copolymers of monomers predominating in vinyl chloride, such as polyvinyl chloride, and the vinyl chloride-vinyl acetate copolymers predominating in vinyl chloride. They may be employed as plasticizers in proportions of from 10 to about 70 parts by weight per parts by weight of poly mer. Their plasticizing efficiency is high and the resulting plasticizide resins have good thermal and light stability, good low-temperature properties, and a low volatility loss.

As disclosed in US. Patent No. 2,863,845, the morpholides of mixed saturated and unsaturated vegetable oil fatty acids are good compatible plasticizers for vinyl chloride resins when the proportions of saturated acids, monoolefinic acids, polyolefinic acids, and epoxidized fatty acids in the mixed acids are such that S/S+M+P+E is about from 1 to 9/100 and P/M-i-P-l-E is less than about 1/ 10. In the foregoing fractions,

Szthe weight of saturated acids in the mixture, Mzthe weight of monoolefinic acids in the mixture, Pzthe weight of polyolefinic acids in the mixture, and Ezthe weight of epoxidized fatty acids in the mixture.

The value of E in the above fractions is zero when no epoxidized fatty acids are present. The term epoxidized fatty acids is used to designate C to (I alkanoic and alkenoic acids containing at least one epoxy group. Such acids are produced by the epoxidation of at least one olefinic group of an unsaturated fatty acid.

As will be apparent to those skilled in the art from the context of the specification, the terms polyunsaturated and polyolefinic are used interchangeably therein and in the claims to describe fatty acid acyl groups or moieties involved in the preparation of the morhpholides. The terms monounsaturated and monoolefinic are also used interchangeably to describe fatty acid acyl groups or moieties involved in the preparation of the morpholides.

In copending patent application Serial To. 79,470 filed December 29, 1960, now US. Patent No. 3,066,111, it was further disclosed that the morpholide mixtures obtained by reacting morpholine with mixtures of the fatty acids which occur in selectively hydrogenated cottonseed oil, said morpholide mixtures containing a proportion of saturated, monounsaturated, and polyunsaturated acyls; i.e., acyls obtainable from selectively hydrogenated cottonseed oil, such that the acyls are equivalent to a mixture of acids in which S/S-l-M+P is about 25/100 and P/M l-P is less than 1/10 are good compatible plasticizers for vinyl chloride resins.

We have now made the surprising discovery that mixtures of morpholides of vegetable oil fatty acids containing a proportion of saturated, monounsaturated, and polyunsaturated acyl groups such that the acyl mixture is equivalent to a mixture of acids in which P/M-l-P is much larger than 1/ 10 are compatible plasticizers for vinyl resins provided the value of S/S+M+P lies Within a specified range which depends on the value of P/M-i-P and provided also that the saturated acyl groups present in the morpholide mixture are predominantly saturated acyl groups containing from 12 to 18 carbon atoms and that the percentage of saturated acyl groups containing 18 or more carbon atoms in the morpholide mixture amounts to less than about 17% of all the acyl groups in the morpholide mixture. For example, as can be seen from the examples and the drawing (in which drawing, as described below, all compositions within the approximate boundaries of area Mfgc are compatible), mixtures of saturated, monounsaturated, and polyunsaturated morpholides for which P/M +P:25/ 100 (represented by the compositions along the straight line joining x and S) are compatible only between i and ii; that is, only if the value of S/S+M+P lies between about 100 and 60/100 and provided also that the saturated acyls present in the morpholide mixture are predominantly saturated acyls containing from 12 to 18 carbon atoms, and that the percentage of saturated acyls containing 18 or more carbon atoms in the morpholide mixture amounts to less than about 17% of all the acyls in the morpholide. This is surprising since, as is obvious from the drawing, such compatible plasticizing mixtures can be prepared by mixing two incompatible plasticizers; i.e., for example, by mixing equal Weights of the compositions represented by S and x, each of which is incompatible, or in general, by mixing the compositions represented by S and x in any proportion between about 1 and 6 parts by weight of x to 4 parts by weight of S.

Similarly we have also discovered that mixtures of morpholides of vegetable oil fatty acids in which S/S-l-M-l-P is much larger than 100 are compatible vinyl plasticizers provided the ratio P/ M -]P lies within a specified range of values and provided also that the saturated acyls present in the morpholide mixture are predominantly saturated acyls containing from 12 to 18 carbon atoms and that the precentage of saturated acyls containing 18 or more carbon atoms in the morpholide mixture amounts to less than about 17% of all the acyls in the morpholide mixture. This is surprising since it shows, as can be seen from the drawing, that compatible plasticizers represented by the compositions within area Mfgc can be obtained my mixing (in appropriate proportions) two incompatible plasticizers, e.g., those represented by compositions in areas Mrfa and cgS, respectively.

We have also discovered that mixtures of the morpholides of saturated, polyunsaturated, and epoxidized fatty acids in which S/S+M+P+E is much larger than 9/100 and P/M-l-P-I-E is much larger than 1/10 but which are compatible vinyl chloride resin plasticizers can be made by mixing two incompatible morpholide mixtures, provided that the saturated acyls present in the morpholide mixture are predominantly saturated acyls containing from 12 to 18 carbon atoms, and that the percentage of saturated acyls containing 18 or more carbon atoms in the morpholide mixture amounts to less than about 17% of all the acyls in the morpholide mixture. For example, the composition represented by Example 43, for which P/P+E=about 100 and the composition represented by Example 40, for which S/S-f-P+E=about 75/100 are individually incompatible, but a mixture of equal parts of these compositions (Example 46), for which E/E+5=54/100 and E/P-|-E=72/100 is compatible.

The mixed morpholides of this invention comprise the morpholides of mixed saturated and unsaturated fatty acids, in which mixture of acids, the weight proportions of saturated acids (S), monoolefinic acids (M), and polyolefinic acids (P), are such that the following conditions are satisfied: (1) that S/S-I-P is greater than about 50/100 (i.e., that the composition lies within area MeS in FIGURE 1), (2) that M/S-l-M-f-P is greater than about 30/100 (i.e., that the composition lies within area Mbc), and (3) that P/M-l-P is less than about /100 (i.e., that the composition lies Within area Mas), excluding those mixtures wherein S/S-l-M-l-P is about from 1/100 to 9/100 and P/M-i-P is less than about 1/10 (i.e, excluding those compositions lying within the approximate area Mrk of the drawing) and excluding the morpholides of selectively hydrogenated cottonseed oil fatty acids, the selective hydrogenation being performed under conditions which result in reducing the proportion of polyolefinic acyls in the mixture by converting the polyole finic acyls to monoolefinic acyls without substantially increasing the proportion of saturated acyls in the mixture, said morpholide mixture consisting of the morpholides of monoolefinic fatty acids (M), polyolefinic fatty acids (P), and saturated fatty acids (S), said saturated fatty acids (S) being present in an amount ranging from about 23/ to 28/ 100, and in which morpholide mixture the proportion of the polyolefinic fatty acyls based on the total unsaturated acyls is such that P/M-l-P is less than 1/ 10 by Weight (i.e., excluding those compositions lying approximately on the line ny of the drawing); provided also that the saturated acyls present in the morpholide mixture are predominantly saturated acyls containing from 12 to 18 carbon atoms, and that the percentage of saturated acyls containing 18 or more carbon atoms in the morpholide mixture amounts to less than about 17% of all the acyls in the morpholide mixture. Thus, the mixed morpholides of this invention comprise compositions represented by all compositions within the area krfgc in the drawing except along my; that is, the area which is common to the areas Mes, Mbc, and MaS, excluding those within the area Mrk and along line my.

The morpholides of this invention also include the morpholides of epoxidized fatty acids. They also include the morpholides of mixtures of epoxidized fatty acids with saturated acids and/or polyunsaturated fatty acids in which mixtures of acids, the weight proportions of saturated acids (S), epoxidized acids (E), and polyunsaturated acids (P), are such that the following conditions are satisfied: (1) that E/S-l-E is greater than about 50/100; (2) that E/P+E is greater than about 70/100; and 3) that the saturated acids present in the mixture of acids are predominantly saturated acids containing from 12 to 18 carbon atoms and the percentage of saturated acids containing 18 or more carbon atoms in said mixture of acids is less than about 17% of all the acids in the mixture.

While the morpholides of this invention can be produced in a variety of ways, they are preferably produced by reacting the mixed acid with m-orpholine. The mixed acids are preferably produced by saponifying a natural glyceride, acidifying the resulting salts and, if necessary, adjusting the composition of the resulting acid mixture so as to obtain a suitable composition which when reacted with morpholine will result in a compatible plasticizer (1) by known procedures for reducing the proportion of saturated acyls such as fractional crystallization or distillation, and/or (2) by converting polyunsaturated acyls to monounsaturated acyls, epoxyalkenoic acyls or epoxyalkanoic acylsthe corresponding morpholides of which are themselves compatible plasticizerssuch as by hydrogenation, halogenation, formylation, dimerization, or epoxidation, etc., and/or (3) by admixing with other fatty acid mixtures and/or with pure fatty acids. Alternatively, the fractionation, hydrogenation, epoxidation or mixing, etc., may be performed on the materials separately or combined which are capable of yielding the desired acid composition or on the corresponding morph-olides or mixed morpholides. In general, it is usually preferred to perform epoxidation at the morpholide stage.

The necessary adjustment can readily be deduced from the drawing and from a knowledge of the proportions of S, M. and P acyls in the given mixture as determined by standard analytical procedures. For example, consider a mixture of vegetable oil fatty acids in which the weight proportions are such that S/S-l-P is about 35/ 100; P/M-l-P is about 65/100; M/S-l-M-l-P is about 25/100; and in which the predominant saturated fatty acid is the C acid with very small amounts of the C and C acids. The drawing shows that the mixed morpholides made from this mixture (represented approximately readily converted to a suitable mixture of acids (i.e., to by w in FIGURE 1) would be incompatible. The drawing also shows that this mixture of fatty acids can be a composition represented by points within area Mfgc),

which when reacted with morpholine will result in a compatible plasticizer; for example, by converting some or all of the polyunsaturated acyls to monounsaturated acyls by such procedures as hydrogenation, halogenation, formylation, dimerization, maleination, etc., so that S/S+P is greater than about 50/100, M/S+M+P is greater than about30/100, and P/M +1 is less than about 40/100.

The composition of the morpholide mixtures of this invention which contain no epoxidized acyl are represented by all compositions within the area Mfgc in the drawing; that is, within the area bounded approximately by M fg, and go. The boundaries M g and go are only approximate. Thus the composition of Example which lies near the boundary outside this area was compatible. Slightly incompatible compositions lying close to but outside the boundaries Mf, fg and go and even less compatible compositions may be used satisfactorily as primary plasticizers in polyvinyl chloride resin formulations containing lower percentages of plasticizer and/or as secondary plasticizers admixed with a suitable compatibilizing plasticizer such as the morpholide of epoxidized fatty acids or compatible mixture of the morpholides of epoxidized fatty acids and/or monounsaturated fatty acids and/ or polyunsaturated fatty acids and/ or saturated fatty acids. Similarly incompatible morpholide mixtures containing the morpholides of epoxidized fatty acids can be used as secon ary plasticizers with compatible morpholide compositions which lie within the area Mfgc in the drawing.

The proportion of the saturated fatty acyls having 18 or more carbon atoms in the chain which can be present in the saturated acyl fraction without causing inconpatability will vary with the overall composition of the morpholide mixture particularly the relative proportions of saturated, monounsaturated, and polyunsaturated acyls present in the mixture. It can be determmined for a given overall composition by evaluating the performance of a series of samples which differ only in the proportion of the C or longer-chain saturated fatty acyls in the saturated fatty acyls present.

We have also discovered that the morpholides of epoxidized fatty acids, i.e., of C to C alkanoic or alkenoic acids containing at least one epoxy group, are compatible, highly efficient, promary plasticizers for vinyl chloride resins and impart to the plasticized resin 21 high degree of stability against heat and light. They are ellicient stabilizers for vinyl chloride resins. We have also discovered that morpholide mixtures such as can be made by mixing even as much as about one part of the morpholide of palmitic acid with one part of the morpholide of epoxidized fatty acids or by mixing as much as about 3 parts of the morpholide of polyunsaturated fatty acids with 7 parts of the morpholide of epoxidized fatty acids are also compatible vinyl chloride resin plasticizers and have the advantage that the plasticized resin has increased thermal stability.

Morpholide mixtures which can be prepared by mixing in any proportion any of the compatible morpholide compositions within the area Mfgc in the drawing with either the morpholides of epoxidized fatty acids or with any mixture of morpholides of fatty acids containing the morpholide of epoxidized fatty acids which mixture of morpholides is itself a compatible vinyl chloride plasticizer are also compatible vinyl chloride plasticizers imparting good thermal stability to the resin. In making such compatible morpholide mixtures the morpholides of epoxidized fatty acids may be introduced by addition or they may he formed in situ; for example, by epoxidizing some of the morpholides of the monaunsaturated or polyunsaturated fatty acids in a given morpholide mixture.

The following examples numbered 1 through 46, the data for which are listed singly in tabular form but 5 which may be considered individually or in related groups for discussion purposes, will demonstrate several of the manifold expressions of our invention.

Various morpholide mixtures were tested as plasticizers for a vinyl chloride-vinyl acetate (955) copolymer resin in a standard formulation comprising: 63.5% resin, 35% plasticizer, 0.5% stearic acid, and 1.0% basic lead carbonate. This formulation for each morpholide sample was milled, molded, and tested. In all examples, the sample was rated as incompatible if the molded stock showed any evidence of exudation or migration to the surface during a shelf storage for days.

The morpholide mixtures used in Examples 1 to 19 were ternary composition-s prepared by mixing appropri ate proportions of the morpholide of oleic acid, the morpholide of linoleic acid, and the morpholide of palmitic acid. The approximate compositions and the results of the compatibility test for these sample are given in Table I and plotted as points in the ternary weight-composition diagram in the drawing. In this figur compatible morpholide mixtures are repersented by open circles and incompatible mixtures by black circles. In Tables 1, M, S, and P represent the weight percent of the morpholides of oleic, palmitic, and linoleic acids comprising the morpholide mixture, respectively.

TABLE I t Ex- M, S, l P, Comamplo Per- Per- Per- IWS+M+P P/M-l-P SIS-i-P pati- No. cent cent cont bility 1 00. 5 38. 1 1. 3 61/100 2/100 97/100 0 51. 2 d7. 7 1. 1 51/100 2/100 08/100 C 78. 0 14. 5 0. 8 79/100 8/100 68/100 0 71. 4 10. 2 9. 3 71/100 12/100 07/100 C 80. 7 0. 8 9. 5 81/100 11/100 51/100 C 37. 2 61. 0 0. 8 37/100 2/100 09/100 C 15. 0 38. 4 16. 5 45/100 27/100 70/100 0 45. 5 42. 0 12. 3 46/100 21/100 77/100 C 35. 1 43. 2 21. 5 /100 38/100 67/100 C 20. 3 57. 4 16. 1 26/100 38/100 78/100 C 53. 8 21. 2 21. 9 54/100 20/ 100 52/100 0 6 10. 3 10. 9 04/100 21/100 53/100 C 70.0 11. 2 18.8 70/100 21/100 37/100 I 70. 0 15. 0 15. 0 70/100 18/100 50/100 0 43. 4 0 20. 0 43/100 32/100 64/100 C 45. 3 40. l 14. 6 /100 24/100 73/100 C 10. 5 30. 0 20. 5 41/100 42/100 /100 I 1 G =compatible; I=incompatiblc.

The sample used in Example 20 was the morpholide of a mixture of fatty acids having the following composition: 10% myristic, 43% pahnitic, 9% stcaric, 30% oleic, and 8% linoleic acids.

The sample used in Example 21 was the morpholide of a mixture of fatty acids having the following composition: 2% myristic, 26% palmitic, 16% stearic, 48% oleic and 8% linoleic acids.

The morpholide of rapeseed fatty acids used in Example 22 was prepared from the composite fatty acids which were obtained by saponification and acidification of rapeseed oil and which consisted of approximately 9.6% linolenic acid, 13.3% linoleic acid, 20.4% oleoic acid, 49% erucic acid, and 7.6% saturated fatty acid. The resulting morpholide mixture, for which the composition was such that M/S+M+P:69/100, P/M+P:25/100, and S/S-i-P 25/100, was tested as a plasticizer for the vinyl chloride-vinyl acetate (-5) resin and was incompatiblc.

The morpholide sample of Example 23 was made by adjusting the composition of the morpholide mixture of Example 22. The latter was mixed with an equal part by weight of a morpholide mixture the composition of which was such that M/S+M+P:about 75/100, P/1M+P=about 0 and S/S+P=about /100, resulting in a final mixture for which 114/ S +M +P= about 72/ 100, P/M-H ahout 14/100 and S/S+P:about 59/100. This was found to be a compatible plasticizer for the vinyl chloride-vinyl acetate (95-5) copolymer resin mentioned above.

The compositional data for the morpholide mixtures of Examples 20 to 23 are given in Table II in which table 3 The corresponding data for Examples 24 to 29 are given in Tables III and/ or IV. For these samples, M, E, S, and P represent the approximate weight percent of morpholides of monoolefinic (unepoxidized), epoxidized,

M, S, and P, represent the weight percent of the mor- 5 saturated and polyunsaturated acids, respectively, compholides of monoolefinic, saturated and polyolefinic prising the morp'holide mixtures, in which morpholide fatty acids, respectively, comprising the rnorpholicle mixmixtures the saturated acyls containing 18 or more carture, in which morpholide mixture, the saturated acyls hon atoms amount to less than about 17% of all the acyls containing 18 or more carbon atoms amount to less than in the morpholicle mixture. The morpholide samples of about 17% of all the acyls in the morpholide mixture. Examples 24 and 26 were prepared from the morpholide of linoleic acid and that for Example 25 from the mor- TABLE II phonde of oleic acid by epoxidization with perbenzoic or E M S P Com peracetic acid. The morpholide samples of Examples 27 ample wt. wt. wt M s+1\ +p -pp ,s s+p nand 28 were prepared by epoxidation of the morpholide 5g; S blhtyl of cottonseed oil fatty acids to an oxirane oxygen content of 2.62% and 4.07%; i.e., to an extent equivalent to that 30/100 21/100 89/100 0 necessary to epoxidize about 50% and about 80%, re- 48/100 14/100 85/100 0 spectively, of the total number of double bonds present. 69/100 /100 25/100 I 72/100 14/100 59/100 0 The morpholide sample of Example 29 was prepared 20 by mixing the proper proportions of the morpholide mix- C=compatible; I=incompatiblc. ture of Example 28 and the morpholide of selectively hy- Th h i l properties of h vinyl chloridewiny} drogenated cottonseed oil fatty acids. The plasticized acetate copolymer resin plasticized with the morpholide l'esln had a p y hlgh degree thermal Stabllltymixtures of Examples 20 to 23 are shown in Table III. The morphohde mixtures used in Examples 30 0 3 TABLE III Example Tensile 100% Elonga- Brittle -Yola- Qornpat- N 0. Plasticlzer Strength, Modulus, tion, Point, tility ibihty p.s.i. p.s.i. Percent C.

Morpholide ot Animal type acids 2,940 1,390 400 -30 0.62 0 Animal acids.-- 2,050 1,370 300 34 0.36 C Rapeseed oil acids 3, 030 1, 470 400 -53 00 I Adjusted rapeseed oilacids 2,880 1,330 360 3 55 C Epoxyoleic acid 3,030 1,270 300 -16 O Epoxystearic acid 2,850 1,300 350 28 0.54 C Diepoxystearic aci 2, 950 1,330 350 -16 0.49 O Partially epoxidized cotton- 2, 940 1,210 400 -26 0.73 0

seed oil acids. Fully epoxidized cottonseed 2,990 1,310 360 22 0.72 C

oil acids.

1 O compatible: I=i11compatible.

for which the compatibility data are given in Table IV, were prepared by mixing the proper proportlons of the mo h lides ooleic acid e ox oleic acid and almitic TABLE IV 45 P y P The morpholide mixtures used in Examples 37, 38, 39, Exmgple M E S P EIE'FS E/H'E f fi g g 40, 41, 42, and 43 were binary compositions prepared by A mixing appropriate proportions of the morphohde of 0 0 0 100/100 100/100 C epoxyoleic acid with either the morpholide of linoleic 0 100 0 0 100/100 100/100 (3 acid or with the morpholide of palmitic acid. The morg 28 g 8 8 pholide mixtures used in Examples 44, 45, and 46 were 0 75 25 0 C ternary mixtures consisting of equal parts by weight of the g 13 g 8 mixture used in Example 40 and those used in Examples 0 4s 0 55/100 100/100 0 55 41, 42, and 43, respectively. The compositions and the 8 g3 23 g results of the compatibility tests for these samples are 17.7 20.8 55.2 0 0 given in Table IV. The sample of Example 46 was a i; g 96 8 8 compatible vinyl chloride plasticizer through it was made 0 40 0 I by mixing the samples of Examples 40 and 43 both of 3 28 9,3 8 60 which were incompatible. 0 2s 75 0 I We claim: 8 Z3 8 53 g I. The morpholide of epoxyoleic acid. 0 0 35 I 2. The morpholide of epoxystearic acid. 8 2 ,2 23 1188 234188 8 3. The morpholide of a diepoxystearic acid. 0 45 37.5 17.5 54/100 72/100 0 69 References Cited by the Examiner 1 Compositions containing the morpholides of both monounsaturated fatty acids and c zoxidized trl'atty atfzidts, and wrliliclhdcan bet prepsred1 by} UNITED STATES PATENTS mixing appropria e propor ions 0 W0 morp o 1 e mix ures eac o which is a compatible vinyl chloride plasticizer. 2863845 12/1958 Magma et 260 30A 2 Compjositirans contiiiniig} tile mogpholidies (if bkpth mgnounsaturiatled 3,066,111 11/1962 Magne et al 26U*30.4 fatty aci s an epoxi ize a y aci s, an w ie can e prepare y 4 mixing two morpholide mixtures each of which is an incompatible vinyl 70 3979988 2/1963 DHPPY et 260 247'7 chloride plasticizer. For example the sample of Example 36 can be pre- 3,081,304 3/ 1963 Rogler 260247.7 pared by mixing equal partfs 55y weightfoittwo inconltpafiiblt morpholide mix ures, one consisting 0 parts 0 e morpoii e o a monounsaturated acid and parts of the morpholilde (if palmitlic aciddanddthe NICHOLAS 8- RIZZO, Pnmary Exammer. other consisting o 35 parts 0 t 1e morp ioli e o epoxyo eie aci an 65 Y parts of the morpholide of palmitic acid. WILLIAM H. SHORT, A. H. BRODMOCKEL,

3 C=compatible; I=inc0rnpatible. 75 Examiners 

1. THE MORPHOLIDE OF EPOXYOLEIC ACID. 